EP0497706A1 - Durch Wärme formbare Zusammensetzungen, Verfahren zu ihrer Herstellung und ihre Anwendung zur Herstellung von thermogeformten Gegenständen - Google Patents

Durch Wärme formbare Zusammensetzungen, Verfahren zu ihrer Herstellung und ihre Anwendung zur Herstellung von thermogeformten Gegenständen Download PDF

Info

Publication number
EP0497706A1
EP0497706A1 EP92400257A EP92400257A EP0497706A1 EP 0497706 A1 EP0497706 A1 EP 0497706A1 EP 92400257 A EP92400257 A EP 92400257A EP 92400257 A EP92400257 A EP 92400257A EP 0497706 A1 EP0497706 A1 EP 0497706A1
Authority
EP
European Patent Office
Prior art keywords
salt
composition according
starch
acid
treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92400257A
Other languages
English (en)
French (fr)
Other versions
EP0497706B1 (de
Inventor
Guy Fleche
Serge Gosset
Morand Lambla
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roquette Freres SA
Original Assignee
Roquette Freres SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roquette Freres SA filed Critical Roquette Freres SA
Publication of EP0497706A1 publication Critical patent/EP0497706A1/de
Application granted granted Critical
Publication of EP0497706B1 publication Critical patent/EP0497706B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
    • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret

Definitions

  • the present invention relates to a new thermoformable composition. It also relates to a new process for preparing a thermoformable composition as well as the use of said composition with a view to obtaining thermoformed articles.
  • thermoforming techniques that is to say of making shapes by the action of temperature
  • synthetic materials such as polyethylene, polypropylene, polystyrene or polyvinyl chloride.
  • synthetic materials are, for example, used for the preparation of articles of all shapes (sheets, tubes, rods or more elaborate shapes) and destinations, such as packaging (garbage bags or containers), cultivation mulches , bottles, certain consumer items (glasses, lots, sheets), etc.
  • a first technology for example described in patent FR 2252385, consists in introducing into a polyolefinic material, constituted in particular by polyethylene, starch granules at a rate generally between 5 and 30%, more particularly of the order of 15%.
  • the starch therein plays a role of uniformly dispersed filler in the polyethylene material. No interaction takes place between the very hydrophilic starch and the very hydrophobic polymer.
  • Starch is added either directly into the polyethylene, or more commonly through a masterbatch that can contain up to 50% starch.
  • the starch is generally dehydrated (humidity less than 1%) and a variant of the process, described in patent GB 1487050, envisages the prior coating of the granule with hydrophobic silyl groups in order to increase the starch-polyethylene compatibility. Sometimes a starter-inducing photodegradation system is added to the starch, thus making it possible to combine bio and photodegradation.
  • Starch provides specific functional properties such as anti-blocking, better printability, anti-static ... in molded or filmed articles, with, however, a reduction in mechanical properties in the case of films.
  • a second technology for example described in patents EP 32802 and EP 132299, consists, with a view to obtaining flexible films, of introducing a continuous phase of starch into a synthetic polymer in order to constitute a structure which is could qualify as composite.
  • the starch granule disintegrated by gelatinization or extrusion is, as described in patent EP 32802, dispersed in a synthetic polymer of hydrophilic nature such as the ethylene-acrylic acid copolymer (EAA), partially neutralized, optionally in the presence of a plasticizer such as glycerol or ethylene glycol.
  • EAA ethylene-acrylic acid copolymer
  • This technique allows the introduction of 50 to 60% starch.
  • the starch-synthetic polymer composite thus obtained is presented as making it possible to manufacture extruded films whose mechanical resistance is improved and showing better biodegradability.
  • the starch is gelatinized in the presence of water and the humidity of the mixture must be lowered in the range 2-10% before the molding or extrusion operations.
  • thermoformable material based essentially on starch is aimed at obtaining thermoformable material based essentially on starch.
  • the starch must be in the form of granules which are destructured by fusion. Its implementation can then be carried out on conventional equipment for processing plastics. It is generally necessary to add, during this treatment, a starch plasticizer system.
  • the finished products obtained consisting essentially of starch, are by nature biodegradable.
  • thermoformable material with a high starch content as described in patent EP 118240 requires rather high temperature and pressure ranges (temperatures above 120 ° C. and pressure of several hundred bars) to satisfy the conditions of transformation into an injection machine.
  • the articles, in particular the capsules, obtained after molding and cooling are however rigid, very fragile and hygroscopic, and their properties mechanics vary with their water content.
  • thermoformable material which is simple, inexpensive, in particular in energy, which does not give rise to any real problem of degradability and which is applicable to the manufacture of a wide range of thermoformed articles.
  • thermoformable composition characterized in that it contains at least one starchy compound and at least one salt of hydroxycarboxylic acid.
  • thermoformable composition resides in the fact that the starchy compound contained within said thermoformable composition can be used under temperature and / or pressure conditions significantly less severe than those generally required in industrial practice. and therefore more favorable to the maintenance of its intrinsic properties.
  • thermoformable composition object of the invention can advantageously be presented in a state which one can qualify as "partial melt".
  • This partially molten state differs from the gelatinization of starch and its total fusion.
  • the gelatinization of starch which is obtained through the use of a high proportion of water, leads to the production of colloidal dispersions.
  • the total melting of the starch is essentially obtained by heat treatment and leads to the complete disappearance of the starch grains.
  • the partial molten state corresponds to an intermediate state in which at least partial destruction of the intermolecular hydrogen bonds is observed, with the establishment of new hydrogen bonds between the water and the hydroxyl groups of the starch. In this intermediate state, the persistence of a certain proportion of starch granules is generally observed.
  • thermoformable compositions in accordance with the invention which make it possible to obtain, including for a thermoforming device and given operating parameters, formed articles having a very wide range mechanical properties, especially in terms of viscoelasticity.
  • the Dynamic Mechanical Analysis technique makes it possible to determine the variation of the loss factor tg ⁇ of a given material over a range of temperatures and in particular to know the temperature at which said material , which is tested as a sample of given dimensions, has a factor maximum tg ⁇ loss. The temperature thus determined makes it possible to approach the glass transition temperature of said material.
  • compositions in accordance with the invention make it possible, as described in more detail below in terms of the examples, to obtain thermoformed articles having a maximum loss factor tg ⁇ lying in a very wide range temperatures, in particular between 0 and 160 ° C., that is to say in the range encompassing the glass transition temperatures of most traditional synthetic polymers.
  • thermoformable composition which is the subject of the invention, which contains at least one starchy compound and at least one salt of hydroxycarboxylic acid, is further characterized by the fact that it is capable of providing a thermoformed article having a factor loss tg ⁇ whose maximum value is at a temperature at most equal to 150 ° C. especially between 0 and 130 ° C approximately.
  • starchy compound within the meaning of the present invention, is meant any type of starch, whatever its origin, native or modified, chemically and / or physically.
  • a native starch is chosen in particular from the group comprising native, natural or hybrid starches, originating from corn, from corn with a high amylopectin content ( waxy starch), high amylose corn, wheat, rice, peas, potato, cassava, cuts or fractions that can be made or obtained and any mixtures of at least two any of the above products.
  • a chemically modified starch is used for the constitution of the conforming compositions in the invention, this is chosen in particular from the group comprising starches modified by at least one or other of the known techniques of etherification, esterification, crosslinking, oxidation, alkaline treatment, acid and / or enzymatic hydrolysis.
  • starches etherified by ionic, in particular cationic, or nonionic groups the latter possibly consisting of hydroxyalkylated starches such as hydroxypropylated or hydroxyethylated starches.
  • starches with a high amylose content native or modified, in particular such cationized starches.
  • starches which have been physically modified beforehand, for example by microwave or ultrasonic treatment, by extrusion cooking, by gelatinization on a drum or by compacting, said starches advantageously being in a state of modification not going beyond the partial fade state described above.
  • chemically modified starches such as those described above may, simultaneously, before or after the chemical modification process, have been subjected to such a physical modification treatment.
  • hydroxycarboxylic acid means any acid comprising at least one hydroxyl function and at least one carboxylic function.
  • the hydroxycarboxylic acid salt which is used in the composition which is the subject of the invention may in particular be chosen from the group comprising the salts of monohydroxy / monocarboxylic acids and the salts of polyhydroxy / monocarboxylic acids, in particular the salts lactic acid, gluconic acid, maltobionic acid, lactobionic acid or glyceric acid, as well as any mixtures of at least any two of said salts.
  • the salts used are preferably those associating hydroxycarboxylic acid with an alkali or alkaline-earth metal, in particular with a metal chosen from the group comprising sodium, potassium, calcium and magnesium.
  • these may in particular contain a potassium salt of a hydroxycarboxylic acid.
  • the composition according to the invention contains, as the hydroxycarboxylic acid salt, at least one salt of lactic acid, in particular an alkali or alkaline earth metal salt lactic acid and in particular sodium lactate or potassium lactate.
  • hydroxycarboxylic acid salt may, although it is not preferred, be generated "in situ", that is to say by bringing together, within the composition according to the invention, a hydroxycarboxylic acid such as lactic acid and an appropriate base (sodium hydroxide, potassium hydroxide, lime, amine) taking care to avoid, contrary to the teachings of patent EP-A-0 282 451 mentioned above, any acid catalysis capable of substantially depolymerizing the starchy compound.
  • a hydroxycarboxylic acid such as lactic acid and an appropriate base (sodium hydroxide, potassium hydroxide, lime, amine) taking care to avoid, contrary to the teachings of patent EP-A-0 282 451 mentioned above, any acid catalysis capable of substantially depolymerizing the starchy compound.
  • the composition in accordance with the invention has a weight ratio between starchy compound (s) on the one hand and hydroxycarboxylic acid salt (s) on the other hand between approximately 99/1 and 25/75 and more preferably between 98/2 and 60/40, it being specified that account is taken, as regards the hydroxycarboxylic acid salt or salts, of the dry weight used.
  • the composition according to the invention can contain one or more adjuvants, of all kinds and functions (extension or bulking agents, synthetic resins, plasticizers, lubricants, coloring agents or the like), for example one or more of the adjuvants described more particularly in the above-mentioned patent EP 118 240
  • adjuvants such as sorbitol, urea, glycerol, their derivatives, or alternatively to any mixtures of those -this.
  • the water content of the composition which is the subject of the invention is not a paramount parameter with a view to its application to the supply of thermoformed articles. In particular, there is no need to adjust this water content, in particular at low levels as described in certain aforementioned publications of the prior art.
  • composition has a humidity such that its supply at the level of the subsequent processing devices can be adequately ensured.
  • this humidity is at most equal to approximately 40% and is in particular between approximately 5 and approximately 30%.
  • thermoformable composition characterized in that one subjects a starchy compound, in the presence or not of a hydroxycarboxylic acid salt and / or one or more adjuvants of all kinds, to a treatment capable of bringing it into a partially molten state and that, optionally, the partially molten starchy compound thus obtained is subsequently placed in the presence of at least one acid salt hydroxycarboxylic and / or one or more adjuvants of all kinds.
  • the treatment to which the starchy compound is subjected can be performed on all types of conventional devices, in particular those conventionally used for application, to products of all kinds, microwaves or ultrasound and / or used for the processing, continuously or discontinuously, of plastics and elastomers and in particular devices of the single-screw or twin-screw extruder type, kneaders or injection molding machines.
  • modules such as the co-kneaders type MDK / E 46 or MDK / E 70 sold by the company BUSS.
  • the treatment to which the starchy compound is subjected is carried out under conditions such that said starchy compound does not undergo substantial depolymerization.
  • the treatment to which the starchy compound is subjected can for example be either a heat treatment, combining or not combining the action of ultrasound and / or pressure with that of temperature, in particular a baking-extrusion or gelatinization treatment on a drum, ie a microwave treatment.
  • thermoformable starchy compositions can now be prepared under operating conditions, in particular of temperature and / or pressure, significantly less severe than those generally required in industrial practice. and therefore more favorable for maintaining the intrinsic properties of the starchy compounds used.
  • the heat treatment, in particular of baking-extrusion, to which the starchy compound can be subjected is carried out at a temperature at most equal to approximately 130 ° C., being in particular between 50 and 120 ° C. approximately.
  • thermoformable composition in accordance with the invention, the treatment to which the starchy compound is subjected in order to bring it into a partially molten state is carried out in the absence of a hydroxycarboxylic acid salt, the compound partially melted starch obtained subsequently being brought into contact, by any appropriate means, of at least one salt of hydroxycarboxylic acid, the latter possibly, although this being not preferred, being generated in situ within the resulting composition.
  • the treatment to which the starchy compound is subjected in order to bring it into a partially molten state is carried out in the presence of at least one salt of hydroxycarboxylic acid, said salt also being able to be generated in situ at within the resulting composition.
  • thermoformable composition in accordance with the invention, the use and the bringing together of the starchy compound, the hydroxycarboxylic acid salt and any adjuvants may be present. perform according to a multitude of variants, in particular with regard to the form of introduction (liquid, viscous or solid form, introduction by intimate mixing or by spraying, etc.) and the moment of introduction (introduction from the start or fractionated in time) of each of these constituents within the composition.
  • the bringing together of the starchy compound and the hydroxycarboxylic acid salt can be carried out by simple restart under temperature conditions which can be described as low , i.e. at most equal to 50 ° C, including close to or below ambient temperatures (20-30 ° C).
  • starchy compound contained in said mixture has previously been destructured by a method as described in patents EP 118 240, EP 282 451, EP 326 517 or EP 327 505 mentioned above.
  • thermoformable starchy compositions obtained in accordance with the invention which constitute new industrial products, can be applied to the preparation of articles of all forms (rods, tubes, sheets, films, granules, capsules, or more forms ), and from all destinations, by using any available thermoforming technique and in particular by extrusion, coextrusion, injection molding, blow molding or calendering.
  • thermoformable compositions are manifested, inter alia, by the possibility of obtaining, including for a thermoforming device and given operating parameters, formed articles having a very wide range of properties mechanical, in particular in terms of viscoelasticity.
  • the estimation of said mechanical properties may in particular consist in the use of the technique known as Dynamic Mechanical Analysis as described in the examples which follow and which state certain advantageous embodiments of the present invention.
  • composition obtained as described above is at ambient temperature, for example, introduced into the feed hopper of a BUSS PR 46 co-kneader type transformation machine.
  • thermoformed articles obtained in this case can be used as is. However, in general, they are more likely to be used for the subsequent feeding of other processing devices, continuous or discontinuous, such as injection presses, single or twin screw extruders, calenders, for the manufacture of finished objects such as tubes, profiles, films, plates, injected parts.
  • Dynamic Mechanical Analysis is a method particularly sensitive to any change in the structure and macromolecular interactions which induces a modification of the macroscopic properties of the material. It is a very fine technique for determining the variation of elastic and loss moduli of a sample as a function of temperature. The same technique also gives access to the glass transition temperature (Tg) of the material. Knowledge of this data as well as the damping properties measured in the solid state can be used to predict the temperature of use, the impact properties as well as the rigidity of the finished product.
  • Tg glass transition temperature
  • the principle of Dynamic Mechanical Analysis is based on the application to a sample of a sinusoidal linear deformation (or torsion) of given frequency and low amplitude superimposed on a constant stress of known value.
  • the response of the material is a stress of the same pulsation but phase shifted by an angle ⁇ .
  • the phase shift angle ⁇ is such that tg ⁇ , also called the loss factor, is equal to E ⁇ / E ′.
  • a purely elastic material such as steel will reveal a zero phase angle, that is to say a zero imaginary component.
  • a purely viscous material such as water will show a real zero component.
  • the phase shift angle will then be 90 °.
  • a viscoelastic material may cover all the values between 0 and 90 °.
  • the tests were carried out on a device of type RSA II (Rheometrics Solid Analyzer).
  • the measurement geometry is the cylindrical tension / compression and temperature sweeps are carried out at constant stress frequency.
  • a measurement is made every 2 ° C, while leaving the sample a time of 2.5 min. in order to ensure its balance thermal with the oven.
  • a starchy composition is produced, by simple mixing, from 80% by weight of native potato starch (water content: approximately 20%) to which 20% by weight of water is added.
  • control composition 1 Said composition (hereinafter referred to as control composition 1) is introduced, directly after its preparation, into the hopper of a BUSS PR 46 co-mixer and then treated in accordance with EXAMPLE 1B above in order to obtain a thermoformable composition and then a thermoformed article of the rush type.
  • FIG. 1 represents, for this sample, the evolution of the loss factor tg ⁇ as a function of the temperature.
  • the curve thus obtained has a maximum of tg ⁇ located at high temperature, of the order of about 130 ° C and this, after a wide range of temperatures where the loss factor is almost zero, the elastic modulus E ′ being much higher than the viscous module E ⁇ .
  • compositions are prepared, referenced 2 to 16, containing at least one starchy compound and at least one salt of hydroxycarboxylic acid, in this case sodium lactate.
  • Table 1 shows for each of said compositions the nature and the rate of introduction (% by weight) of each of the components used (starchy compound, hydroxycarboxylic acid salt, optional adjuvant (s).
  • compositions are introduced, directly after their preparation, into the hopper of a BUSS PR 46 co-mixer and then treated in accordance with EXAMPLE 1B above in order to obtain thermoformable compositions and then thermoformed articles of the rush type. .
  • Table 2 shows, for each of the compositions according to the invention 2 to 16, as well as for the control composition 1 tested in the context of EXAMPLE 2, the temperature for which the value of the loss factor tg ⁇ , measured by Dynamic Mechanical Analysis, is maximum.
  • thermoformable compositions according to the invention allow the preparation of thermoformed articles having a wide range of mechanical properties.
  • FIG. 2 in particular shows that the combination of a starchy compound such as potato starch with a hydroxycarboxylic acid salt such as sodium lactate, in accordance with the invention, makes it possible to work under operating conditions , in particular of significantly less severe temperatures than those generally required in the context of obtaining and processing thermoformable starchy materials.
  • compositions 2 and 3 we are witnessing, by adding sodium lactate (compositions 2 and 3) in place of water (control composition 1), a shift in the temperature of the maximum tg ⁇ of the material obtained (130 ° C. approximately) towards significantly lower temperatures, for example 95 ° C or approximately 35 ° C respectively for compositions 2 and 3. It follows, for example, that depending on the rate of introduction of the salt of hydroxycarboxylic acid within the thermoformable compositions according to the invention, it is possible to manufacture materials having a greater or lesser flexibility at room temperature.
  • adjuvants such as urea and / or sorbitol allows an additional adjustment of the viscoelastic properties and of the value of this temperature of the maximum loss factor as it results from the curves taken up at the level of the figure 3.
  • composition 4 allows a temperature of the maximum tg ⁇ to be further lowered (t ⁇ 30 ° C instead of about 35 ° C for composition 3 does not containing no urea).
  • the curves of FIGS. 4 and 5 illustrate the possibility of using starch-forming compositions within the thermoformable compositions according to the invention, in particular those which must be treated at temperatures below about 120 ° C., including below 100 ° C. of great diversity, whether in their origin (potato starch, starch rich in amylose, waxy starch, for example) or in their mode 4th possible modification by chemical means (etherification and / or crosslinking for example) and / or physical.
  • compositions no. 10 to 13 corresponding to FIGS. 6 to 9 illustrate the possibility of using various salts of hydroxycarboxylic acids, all of which lead to a significant decrease in temperature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Pyridine Compounds (AREA)
  • Heat Treatment Of Steel (AREA)
  • Magnetic Resonance Imaging Apparatus (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Thermotherapy And Cooling Therapy Devices (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP92400257A 1991-01-31 1992-01-31 Durch Wärme formbare Zusammensetzungen, Verfahren zu ihrer Herstellung und ihre Anwendung zur Herstellung von thermogeformten Gegenständen Expired - Lifetime EP0497706B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9101120A FR2672295B1 (fr) 1991-01-31 1991-01-31 Compositions thermoformables, leur procede de preparation et leur utilisation pour l'obtention d'articles thermoformes.
FR9101120 1991-01-31

Publications (2)

Publication Number Publication Date
EP0497706A1 true EP0497706A1 (de) 1992-08-05
EP0497706B1 EP0497706B1 (de) 1996-11-13

Family

ID=9409252

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92400257A Expired - Lifetime EP0497706B1 (de) 1991-01-31 1992-01-31 Durch Wärme formbare Zusammensetzungen, Verfahren zu ihrer Herstellung und ihre Anwendung zur Herstellung von thermogeformten Gegenständen

Country Status (18)

Country Link
US (1) US5360473A (de)
EP (1) EP0497706B1 (de)
JP (1) JPH04311738A (de)
KR (1) KR920014864A (de)
CN (1) CN1063699A (de)
AT (1) ATE145216T1 (de)
AU (1) AU652796B2 (de)
BR (1) BR9200317A (de)
CA (1) CA2060409A1 (de)
DE (1) DE69215121T2 (de)
DK (1) DK0497706T3 (de)
ES (1) ES2095421T3 (de)
FI (1) FI920439A7 (de)
FR (1) FR2672295B1 (de)
HU (1) HUT60308A (de)
IE (1) IE920316A1 (de)
NO (1) NO920401L (de)
ZA (1) ZA92645B (de)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0580032A1 (de) * 1992-07-15 1994-01-26 SOLVAY (Société Anonyme) Bioabbaubare Formzusammensetzungen, enthaltend thermoplastische Stärke und thermoplastischen aliphatischen Polyester
EP0579546A3 (en) * 1992-07-15 1994-07-06 Roquette Freres Thermoformable composition, process for its preparation and its use for obtaining thermoformed articles
EP0609983A3 (de) * 1993-02-05 1994-12-21 Cerestar Holding Bv Zusammensetzung auf Basis von Stärke.
US5703160A (en) * 1992-07-15 1997-12-30 Solvay S.A. Biodegradable moulding compositions comprising a starch, a biodegradable polyester, and a salt of a hydroxycarboxylic acid
WO1998034984A1 (en) * 1997-02-10 1998-08-13 Instituut Voor Agrotechnologisch Onderzoek (Ato-Dlo) Agent against retrogradation of starch
EP0936201A3 (de) * 1998-02-11 2000-05-17 Roquette FrÀ¨res Zusatzmittel für anorganische Bindemittel auf Basis von (oxidiertem) Zucker und hydrogeniertem Zucker, diese Zusatzmittel enthaltende anorganische Bindemittel und Verfahren zu ihrer Herstellung
WO2006042364A1 (en) * 2004-10-18 2006-04-27 Plantic Technologies Ltd Barrier film
WO2011086292A1 (fr) 2009-12-22 2011-07-21 Roquette Freres Compositions a base de matiere vegetale et de fibres synthetiques et procede de preparation de telles compositions
US11149144B2 (en) 2015-06-30 2021-10-19 BiologiQ, Inc. Marine biodegradable plastics comprising a blend of polyester and a carbohydrate-based polymeric material
US11359088B2 (en) 2015-06-30 2022-06-14 BiologiQ, Inc. Polymeric articles comprising blends of PBAT, PLA and a carbohydrate-based polymeric material
US11674014B2 (en) 2015-06-30 2023-06-13 BiologiQ, Inc. Blending of small particle starch powder with synthetic polymers for increased strength and other properties
US11674018B2 (en) 2015-06-30 2023-06-13 BiologiQ, Inc. Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics
US11807741B2 (en) 2015-06-30 2023-11-07 BiologiQ, Inc. Articles formed with renewable green plastic materials and starch-based polymeric materials lending increased biodegradability
US11840623B2 (en) 2015-06-30 2023-12-12 BiologiQ, Inc. Methods for lending biodegradability to non-biodegradable polyolefin and nylon materials
US11879058B2 (en) 2015-06-30 2024-01-23 Biologiq, Inc Yarn materials and fibers including starch-based polymeric materials
US11926929B2 (en) 2015-06-30 2024-03-12 Biologiq, Inc Melt blown nonwoven materials and fibers including starch-based polymeric materials
US11926940B2 (en) 2015-06-30 2024-03-12 BiologiQ, Inc. Spunbond nonwoven materials and fibers including starch-based polymeric materials

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5679145A (en) 1992-08-11 1997-10-21 E. Khashoggi Industries Starch-based compositions having uniformly dispersed fibers used to manufacture high strength articles having a fiber-reinforced, starch-bound cellular matrix
US5660900A (en) 1992-08-11 1997-08-26 E. Khashoggi Industries Inorganically filled, starch-bound compositions for manufacturing containers and other articles having a thermodynamically controlled cellular matrix
US5662731A (en) 1992-08-11 1997-09-02 E. Khashoggi Industries Compositions for manufacturing fiber-reinforced, starch-bound articles having a foamed cellular matrix
US5709827A (en) 1992-08-11 1998-01-20 E. Khashoggi Industries Methods for manufacturing articles having a starch-bound cellular matrix
US5810961A (en) 1993-11-19 1998-09-22 E. Khashoggi Industries, Llc Methods for manufacturing molded sheets having a high starch content
BE1006138A3 (fr) * 1992-09-01 1994-05-24 Solvay Compositions polymeriques pour la production d'articles soudables en haute frequence, maitre melange pour la preparation de ces compositions et articles produits a partir de celles-ci.
US5716675A (en) 1992-11-25 1998-02-10 E. Khashoggi Industries Methods for treating the surface of starch-based articles with glycerin
US5736209A (en) 1993-11-19 1998-04-07 E. Kashoggi, Industries, Llc Compositions having a high ungelatinized starch content and sheets molded therefrom
US6083586A (en) 1993-11-19 2000-07-04 E. Khashoggi Industries, Llc Sheets having a starch-based binding matrix
US5705203A (en) 1994-02-07 1998-01-06 E. Khashoggi Industries Systems for molding articles which include a hinged starch-bound cellular matrix
US5776388A (en) 1994-02-07 1998-07-07 E. Khashoggi Industries, Llc Methods for molding articles which include a hinged starch-bound cellular matrix
US5843544A (en) 1994-02-07 1998-12-01 E. Khashoggi Industries Articles which include a hinged starch-bound cellular matrix
US6168857B1 (en) 1996-04-09 2001-01-02 E. Khashoggi Industries, Llc Compositions and methods for manufacturing starch-based compositions
US6231970B1 (en) 2000-01-11 2001-05-15 E. Khashoggi Industries, Llc Thermoplastic starch compositions incorporating a particulate filler component
ATE538082T1 (de) * 2001-10-08 2012-01-15 Purac Biochem Bv Verfahren zur herstellung stabiler, pulverförmiger alkalimetallactate
US20070021515A1 (en) * 2005-07-19 2007-01-25 United States (as represented by the Secretary of Agriculture) Expandable starch-based beads and method of manufacturing molded articles therefrom
US7989524B2 (en) 2005-07-19 2011-08-02 The United States Of America, As Represented By The Secretary Of Agriculture Fiber-reinforced starch-based compositions and methods of manufacture and use
FR2932488B1 (fr) * 2008-06-13 2012-10-26 Roquette Freres Compositions thermoplastiques ou elastomeriques a base d'amidon et procede de preparation de telles compositions.
FR2957928B1 (fr) 2010-03-25 2013-07-05 Roquette Freres Compositions a base de matiere vegetale et procede de preparation de telles compositions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2292005A1 (fr) * 1974-11-22 1976-06-18 Sumitomo Bakelite Co Composition de moulage binaire contenant des proteines et de l'amidon, son procede de preparation, et ses applications
EP0118240A2 (de) * 1983-02-18 1984-09-12 Warner-Lambert Company Spritzgussverfahren zur Formgebung von Stärke
EP0282451A2 (de) * 1987-03-09 1988-09-14 Warner-Lambert Company Verfahren zu Herstellung von destrukturierten Stärke

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50101442A (de) * 1974-01-14 1975-08-12
US4076846A (en) * 1974-11-22 1978-02-28 Sumitomo Bakelite Company Limited Protein-starch binary molding composition and shaped articles obtained therefor
AU5921390A (en) * 1989-05-19 1990-12-18 Agri-Tech Industries, Inc. Injection molded biodegradable starch polymer composite
JPH0725944B2 (ja) * 1989-07-20 1995-03-22 ワーナー・ランバート・カンパニー 変性澱粉を含有する、ポリマーをベースとするブレンド組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2292005A1 (fr) * 1974-11-22 1976-06-18 Sumitomo Bakelite Co Composition de moulage binaire contenant des proteines et de l'amidon, son procede de preparation, et ses applications
EP0118240A2 (de) * 1983-02-18 1984-09-12 Warner-Lambert Company Spritzgussverfahren zur Formgebung von Stärke
EP0282451A2 (de) * 1987-03-09 1988-09-14 Warner-Lambert Company Verfahren zu Herstellung von destrukturierten Stärke

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WORLD PATENTS INDEX Derwent Publications Ltd., London, GB; AN 76-12150X & JP-A-50 101 442 (AZUMA K) 12 Août 1975 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0580032A1 (de) * 1992-07-15 1994-01-26 SOLVAY (Société Anonyme) Bioabbaubare Formzusammensetzungen, enthaltend thermoplastische Stärke und thermoplastischen aliphatischen Polyester
BE1006077A3 (fr) * 1992-07-15 1994-05-10 Solvay Compositions de moulage biodegradables comprenant au moins un amidon thermoplastique et au moins un polyester aliphatique thermoplastique.
EP0579546A3 (en) * 1992-07-15 1994-07-06 Roquette Freres Thermoformable composition, process for its preparation and its use for obtaining thermoformed articles
US5703160A (en) * 1992-07-15 1997-12-30 Solvay S.A. Biodegradable moulding compositions comprising a starch, a biodegradable polyester, and a salt of a hydroxycarboxylic acid
EP0609983A3 (de) * 1993-02-05 1994-12-21 Cerestar Holding Bv Zusammensetzung auf Basis von Stärke.
WO1998034984A1 (en) * 1997-02-10 1998-08-13 Instituut Voor Agrotechnologisch Onderzoek (Ato-Dlo) Agent against retrogradation of starch
EP0936201A3 (de) * 1998-02-11 2000-05-17 Roquette FrÀ¨res Zusatzmittel für anorganische Bindemittel auf Basis von (oxidiertem) Zucker und hydrogeniertem Zucker, diese Zusatzmittel enthaltende anorganische Bindemittel und Verfahren zu ihrer Herstellung
WO2006042364A1 (en) * 2004-10-18 2006-04-27 Plantic Technologies Ltd Barrier film
WO2011086292A1 (fr) 2009-12-22 2011-07-21 Roquette Freres Compositions a base de matiere vegetale et de fibres synthetiques et procede de preparation de telles compositions
US11149144B2 (en) 2015-06-30 2021-10-19 BiologiQ, Inc. Marine biodegradable plastics comprising a blend of polyester and a carbohydrate-based polymeric material
US11359088B2 (en) 2015-06-30 2022-06-14 BiologiQ, Inc. Polymeric articles comprising blends of PBAT, PLA and a carbohydrate-based polymeric material
US11674014B2 (en) 2015-06-30 2023-06-13 BiologiQ, Inc. Blending of small particle starch powder with synthetic polymers for increased strength and other properties
US11674018B2 (en) 2015-06-30 2023-06-13 BiologiQ, Inc. Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics
US11807741B2 (en) 2015-06-30 2023-11-07 BiologiQ, Inc. Articles formed with renewable green plastic materials and starch-based polymeric materials lending increased biodegradability
US11840623B2 (en) 2015-06-30 2023-12-12 BiologiQ, Inc. Methods for lending biodegradability to non-biodegradable polyolefin and nylon materials
US11879058B2 (en) 2015-06-30 2024-01-23 Biologiq, Inc Yarn materials and fibers including starch-based polymeric materials
US11926929B2 (en) 2015-06-30 2024-03-12 Biologiq, Inc Melt blown nonwoven materials and fibers including starch-based polymeric materials
US11926940B2 (en) 2015-06-30 2024-03-12 BiologiQ, Inc. Spunbond nonwoven materials and fibers including starch-based polymeric materials

Also Published As

Publication number Publication date
CN1063699A (zh) 1992-08-19
HU9200279D0 (en) 1992-05-28
HUT60308A (en) 1992-08-28
ATE145216T1 (de) 1996-11-15
FR2672295B1 (fr) 1994-06-03
DE69215121D1 (de) 1996-12-19
NO920401D0 (no) 1992-01-30
BR9200317A (pt) 1992-10-06
FI920439L (fi) 1992-08-01
DK0497706T3 (da) 1997-04-21
ES2095421T3 (es) 1997-02-16
CA2060409A1 (en) 1992-08-01
ZA92645B (en) 1992-10-28
AU652796B2 (en) 1994-09-08
KR920014864A (ko) 1992-08-25
JPH04311738A (ja) 1992-11-04
FI920439A7 (fi) 1992-08-01
FI920439A0 (fi) 1992-01-31
FR2672295A1 (fr) 1992-08-07
DE69215121T2 (de) 1997-06-05
EP0497706B1 (de) 1996-11-13
US5360473A (en) 1994-11-01
IE920316A1 (en) 1992-07-29
AU1059092A (en) 1992-08-06
NO920401L (no) 1992-08-03

Similar Documents

Publication Publication Date Title
EP0497706B1 (de) Durch Wärme formbare Zusammensetzungen, Verfahren zu ihrer Herstellung und ihre Anwendung zur Herstellung von thermogeformten Gegenständen
EP0579546B1 (de) Durch Wärme formbare Zusammensetzung, Verfahren zu ihrer Herstellung und ihre Anwendung zur Herstellung von thermogeformten Gegenständen
EP0735104B1 (de) Verfahren zur Kompatibilisierung von Polymeren
CA1304178C (fr) Compositions a base de polyurethanne permettant l'obtention par calandrage de materiaux biodegradables
Yu et al. Microstructure and mechanical properties of orientated thermoplastic starches
US5703160A (en) Biodegradable moulding compositions comprising a starch, a biodegradable polyester, and a salt of a hydroxycarboxylic acid
EP0599535B1 (de) Material auf Stärkebasis
CA3135264A1 (fr) Article multicouche enzyme
CA2114286C (en) Starch-based material
EP3818099A1 (de) Kunststoffmaterial mit hohem pla-gehalt mit einem citratester
FR3106592A1 (fr) Procédé de Préparation d’un Mélange Maître Enzymé
EP1112319B1 (de) Biologisch abbaubarer werkstoff auf basis eines polymers und getreidemehl, verfahren zur herstellung und verwendungen
US20220064411A1 (en) Compound or film containing thermoplastic starch and a thermoplastic polymer
EP1208149B1 (de) Thermoplastische aliphatische polyesterzusammensetzungen, verfahren zu ihrer herstellung und ihre verwendungen
FR2856405A1 (fr) Materiau biodegradable a base de polymeres et de matieres cerealieres plastifiees, son procedede fabrication et ses utilisations
EP0775720A1 (de) Halbsteife Polycaprolactonfolie und Verfahren zu seiner Herstellung
EP2872564B1 (de) Thermoplastische stärke zusammensetzung die funktionalisiertes polypropylene enthält
FR2697260A1 (fr) Compositions thermoformables biodégradables, leur procédé de préparation et leur utilisation pour l'obtention d'articles thermoformés.
FR3139569A1 (fr) ARTICLE MONOCOUCHE ENZYMÉ ayant des propriétés barrières à l’eau
WO2024056824A1 (fr) Article multicouche enzymé ayant des proprietes barrieres a l'eau
WO2025190969A1 (fr) Article méthanisable enzymé
WO2014009678A1 (fr) Composition thermoplastique à base d'amidon comprenant un polypropylène fonctionnalisé de fluidité sélectionnée
WO2014009677A1 (fr) Composition thermoplastique à base d'amidon comprenant une cire de polyéthylène fonctionnalisée

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU MC NL PT SE

17P Request for examination filed

Effective date: 19921123

17Q First examination report despatched

Effective date: 19950424

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19961113

REF Corresponds to:

Ref document number: 145216

Country of ref document: AT

Date of ref document: 19961115

Kind code of ref document: T

REF Corresponds to:

Ref document number: 69215121

Country of ref document: DE

Date of ref document: 19961219

ITF It: translation for a ep patent filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970131

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: BOVARD AG PATENTANWAELTE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Effective date: 19970213

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2095421

Country of ref document: ES

Kind code of ref document: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19970123

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Effective date: 19970731

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19980119

Year of fee payment: 7

Ref country code: CH

Payment date: 19980119

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19980122

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19980127

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 19980129

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990131

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990131

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990131

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990202

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990131

EUG Se: european patent has lapsed

Ref document number: 92400257.9

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20021029

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20021217

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20021223

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20030108

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20030213

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040202

BERE Be: lapsed

Owner name: *ROQUETTE FRERES

Effective date: 20040131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040803

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040930

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20040801

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050131

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20040202